CN113773632B - Composition containing curable polyphenyl ether resin and application thereof - Google Patents
Composition containing curable polyphenyl ether resin and application thereof Download PDFInfo
- Publication number
- CN113773632B CN113773632B CN202111037930.0A CN202111037930A CN113773632B CN 113773632 B CN113773632 B CN 113773632B CN 202111037930 A CN202111037930 A CN 202111037930A CN 113773632 B CN113773632 B CN 113773632B
- Authority
- CN
- China
- Prior art keywords
- weight
- polyphenyl ether
- curable
- parts
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 275
- 229920005989 resin Polymers 0.000 title claims abstract description 152
- 239000011347 resin Substances 0.000 title claims abstract description 152
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 239000002904 solvent Substances 0.000 claims abstract description 184
- 238000006243 chemical reaction Methods 0.000 claims abstract description 153
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 127
- 238000007598 dipping method Methods 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 71
- 239000011159 matrix material Substances 0.000 claims abstract description 59
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003063 flame retardant Substances 0.000 claims abstract description 31
- 230000009471 action Effects 0.000 claims abstract description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 4
- 238000000518 rheometry Methods 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 118
- 238000003756 stirring Methods 0.000 claims description 98
- 238000006116 polymerization reaction Methods 0.000 claims description 92
- 239000003112 inhibitor Substances 0.000 claims description 87
- 238000012360 testing method Methods 0.000 claims description 55
- 239000003054 catalyst Substances 0.000 claims description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 53
- 150000002989 phenols Chemical class 0.000 claims description 50
- 238000001914 filtration Methods 0.000 claims description 49
- 238000005406 washing Methods 0.000 claims description 49
- 230000001376 precipitating effect Effects 0.000 claims description 48
- 239000003999 initiator Substances 0.000 claims description 45
- 239000011889 copper foil Substances 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000945 filler Substances 0.000 claims description 31
- 239000002981 blocking agent Substances 0.000 claims description 29
- 230000009477 glass transition Effects 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000004744 fabric Substances 0.000 claims description 21
- 230000004580 weight loss Effects 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 18
- 238000003825 pressing Methods 0.000 claims description 18
- 230000003746 surface roughness Effects 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-dimethylaminopyridine Substances CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 4
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- UVTXHAOLTBFLDL-UHFFFAOYSA-N 4-[(4-carboxyphenyl)-phenylphosphoryl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1P(=O)(C=1C=CC(=CC=1)C(O)=O)C1=CC=CC=C1 UVTXHAOLTBFLDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- FFIUNPRXUCRYFU-UHFFFAOYSA-N tert-butyl pentaneperoxoate Chemical compound CCCCC(=O)OOC(C)(C)C FFIUNPRXUCRYFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- LMXRTXPFJNGAAX-UHFFFAOYSA-N bis(3,5-dimethylphenyl)-oxophosphanium Chemical compound CC1=CC(C)=CC([P+](=O)C=2C=C(C)C=C(C)C=2)=C1 LMXRTXPFJNGAAX-UHFFFAOYSA-N 0.000 claims 1
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 67
- 230000000694 effects Effects 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 105
- 230000035484 reaction time Effects 0.000 description 44
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 28
- 238000013007 heat curing Methods 0.000 description 26
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 23
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 16
- 238000010030 laminating Methods 0.000 description 16
- 239000003292 glue Substances 0.000 description 15
- 238000001723 curing Methods 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000008901 benefit Effects 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- MWSOSEYIOCGKDW-UHFFFAOYSA-N 1,1,2-tris(chloranyl)ethene Chemical compound ClC=C(Cl)Cl.ClC=C(Cl)Cl MWSOSEYIOCGKDW-UHFFFAOYSA-N 0.000 description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 4
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- JOTOPCOJPUYXPE-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1.ClC1=CC=CC=C1 JOTOPCOJPUYXPE-UHFFFAOYSA-N 0.000 description 4
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000007342 radical addition reaction Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 4
- DQCMWCVJSOFDSA-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl.CC(Cl)(Cl)Cl DQCMWCVJSOFDSA-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000006254 rheological additive Substances 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000002009 alkene group Chemical group 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- YWLXZCAOJYQMKY-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl.ClC1=CC=CC=C1Cl YWLXZCAOJYQMKY-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical group CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical group CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- CRTMHFYHYMQVSB-UHFFFAOYSA-N CC=1C=C(C=C(C1)C)[P](C1=CC(=CC(=C1)C)C)=O Chemical compound CC=1C=C(C=C(C1)C)[P](C1=CC(=CC(=C1)C)C)=O CRTMHFYHYMQVSB-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920013638 modified polyphenyl ether Polymers 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a composition containing curable polyphenyl ether and application thereof, wherein the composition comprises the following components in parts by weight: curable polyphenylene ether resin: 100 parts; crosslinking agent: 0-10 parts; and (3) filling: 30-70 parts; vinyl-containing silane coupling agent: 0-1 part; flame retardant: 1-20 parts; rheology aid: 0.1-5 parts; solvent: 50-100 parts; the application process of the composition comprises the following steps: transferring the composition to a dipping tank; then the substrate is completely immersed in a gum dipping tank, and the gum solution enters the substrate to finish the gum dipping process under the action of a gum dipping roller in the gum dipping tank; and extruding the impregnated matrix by an extruding roller, and baking at 100-180 ℃ for 1-5 minutes to obtain the prepreg. The lateral group of the molecular structure and the terminal groups of the curable polyphenyl ether resin contained in the composition have curable functional groups, so that the composition has high activity, low reaction temperature, mild crosslinking curing conditions and the like; the prepared copper-clad plate has high crosslinking degree, strong heat resistance, small expansion coefficient and good heat conductivity, and is suitable for preparing high-speed circuit substrates.
Description
Technical Field
The invention belongs to the technical field of polyphenyl ether, relates to a composition containing curable polyphenyl ether resin and application thereof, and particularly relates to application in the aspects of high-heat-resistance, low-expansion-coefficient and high-speed copper-clad plates and packaging substrates.
Background
The realization and development of 5G technology has placed higher performance demands on printed circuit substrate materials. Common circuit substrates (epoxy resin-based FR-4 copper-clad plates and the like) have the defects of high loss, large heating value and unstable transmission on high-frequency signals, and are difficult to meet the application requirements of 5G communication. The PPO (PPO) molecular chain structure is symmetrical, contains a large number of rigid benzene ring structures, has more lateral methyl groups, has rigid molecular chains and no strong polar groups, and the structural characteristics endow PPO resin with high glass transition temperature (220 ℃) and high thermal decomposition temperature (262 ℃), low dielectric constant (2.45@1GHz) and low dielectric loss (0.0007@1GHz), the dielectric constant and the dielectric loss are hardly affected at the temperature of-150 ℃ to 200 ℃ and the frequency of 10Hz to 10GHz, and the water absorption rate is not more than 0.05 percent, so that the excellent characteristics lay the foundation for the PPO resin serving as an electronic material. Therefore, the polyphenyl ether resin is the first resin material for preparing electronic insulating materials and high-frequency and high-speed copper-clad plates. However, the PPO resin is a thermoplastic resin with higher molecular weight, has poor fluidity, does not cure, has poor solvent resistance to chlorinated hydrocarbon, aromatic hydrocarbon and the like, and can be better applied to the preparation of resin-based composite materials such as insulation, high-frequency and high-speed copper-clad plates and the like by performing curable modification.
Chinese patent CN1745142a discloses a polyphenylene ether resin composition with an unsaturated double bond at the molecular chain end, wherein triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC) are used as crosslinking agents, the glass transition temperature of the prepared copper-clad plate is between 218 and 236 ℃, the dielectric constant is between 3.14 and 3.15, the dielectric loss is 0.0015, and the z-axis thermal expansion coefficient is 59 to 61ppm/°c. The patent uses TAIC or TAC as a curing agent, and a large amount of TAIC or TAC can raise the glass transition temperature of the copper-clad plate, but the TAIC or TAC has low reactivity and needs a high temperature for a long time to completely cure the composition. In addition, because of inherent characteristics of TAIC or TAC cross-linking agents, the solidified copper-clad plate has high brittleness, and the processing problems of cracking, broken edges and the like are easy to occur during the later preparation of PCB drilling holes. Chinese patent CN102807658A discloses a low molecular weight polyphenylene ether resin composition having unsaturated double bonds at the molecular chain ends, and prepregs and copper clad laminates prepared from the composition. In order to solve the problem of heat resistance reduction of low molecular weight functionalized polyphenyl ether caused by low molecular weight and the problem of good process processability, the composition uses olefin resin as a curing agent and a peroxide free radical initiator, and the prepared copper-clad plate has a glass transition temperature Tg of 220-240 ℃, a dielectric constant of 3.3-3.7 and a dielectric loss of 0.0035-0.0045.
The high frequency and high speed transmission of signals in 5G communication applications will increase the heat productivity of components such as chips, and the accumulation of heat causes the temperature rise and significant expansion in the thickness direction of the circuit board, which will affect the function of the components and the stability of soldering, and will also affect the stability and reliability of signal transmission, thus the substrate material of the circuit board needs to have high glass transition temperature, high thermal decomposition temperature, low thermal expansion coefficient, good thermal conductivity and excellent processability.
Therefore, the copper-clad plate with higher heat-resistant temperature, lower thermal expansion coefficient and good heat conduction performance is designed, so that the copper-clad plate has very important significance in meeting the application in the field of 5G information communication.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a composition containing curable polyphenyl ether resin and application thereof.
In order to achieve the above purpose, the invention adopts the following scheme:
a composition containing curable polyphenyl ether comprises the following components in parts by weight:
curable polyphenylene ether resin: 100 parts;
crosslinking agent: 0 to 10 parts (when the content of the cross-linking agent is 0, the composition is directly cross-linked and solidified under the action of heat);
And (3) filling: 30-70 parts;
vinyl-containing silane coupling agent: 0-1 part; (when the content of the vinyl-containing silane coupling agent is 0, the filler is directly added, and when the content of the vinyl-containing silane coupling agent is not 0, the filler is firstly mixed with the vinyl-containing silane coupling agent and then added);
flame retardant: 1-20 parts;
rheology aid: 0.1-5 parts;
solvent: 50-100 parts;
in the composition, the molecules of the curable polyphenylene ether resin have the following structure:
wherein R is 1 And R is 2 Each independently selected from formula I or formula II; r is R 3 、R 4 、R 5 And R is 6 Each independently selected from-H or-CH 3 If the terminal group is-H atom, then the benzene rings at the two ends of the molecular chain have no side group with large steric hindrance, so that the reaction activity of the two end groups of the polyphenyl ether molecular chain in the subsequent end capping modification can be further improved, and the reaction of the end capping reagent is facilitated; x is of the structure Or->Wherein R is 12 、R 13 、R 14 And R is 15 Each independently selected from-H, -CH 3 Or an unsaturated vinyl group having 2 to 8 carbon atoms, and R 12 、R 13 、R 14 And R is 15 At least one of which contains an unsaturated olefinic group.
Under the action of heat or initiator, the radical addition reaction can be generated on the radical on the molecular chain side group of the curable polyphenyl ether, and the radical addition reaction and other double bonds in the system generate a crosslinking network structure in or between molecules so as to form three-dimensional crosslinking And a network, which endows the material with organic solvent resistance, high glass transition temperature and heat resistance. R is R 12 、R 13 、R 14 And R is 15 The unsaturated alkene groups contained in the modified polyethylene can be designed and adjusted according to the use requirement, so that the advantages of adjustable double bond content, controllable crosslinking degree, designable material performance and the like are realized; the vinyl groups of the side group structures are nonpolar, no polar groups are generated after crosslinking, the resin does not absorb moisture, the dielectric constant of the cured resin material is between 2.43 and 2.46, the dielectric loss is between 0.0007 and 0.0008, and the resin material has excellent dielectric properties and is suitable for being used under high-speed and high-frequency conditions;
the structural formula I is:
the structural formula II is as follows:
wherein R is 7 And R is 8 In ortho-, meta-or para-position of the benzene ring, R 9 And R is 10 In ortho-, meta-or para-position of the benzene ring, R 7 、R 8 、R 9 And R is 10 Each independently selected from-H or-CH=CH 2 A group, and R 7 And R is 8 Comprises at least one of-CH=CH 2 A group R 9 And R is 10 Comprises at least one of-CH=CH 2 A group; as terminal groups of the chain structure of the curable polyphenylene ether, R 1 And R is 2 Respectively contains at least one-CH=CH 2 The radical can generate free radical addition reaction under the action of heat or initiator, and generates intramolecular or intermolecular cross-linked network structure with other double bonds in the system to form a three-dimensional cross-linked network, so that the material has high organic solvent resistance, high glass transition temperature and high heat resistance. Unlike the prior art where the end groups disclosed in the literature or patents are acrylate groups, the present invention provides a polymer The phenyl ether resin has a curable vinyl group in the middle part of the molecular chain, and vinyl groups at the two end groups of the molecular chain (namely R 1 And R is 2 ) The method has the advantages of high activity, low reaction temperature, mild and controllable crosslinking and curing conditions and the like. In order to further improve the thermal properties such as glass transition temperature, heat resistance and the like of the cured material, R 7 、R 8 Can be all-CH=CH 2 The advantages of adjustable double bond content, controllable crosslinking degree, designable material performance and the like are realized; the vinyl groups of the end groups are nonpolar, no polar groups are generated after crosslinking, the resin is not hygroscopic, the dielectric constant and dielectric loss of the cured material are low, and good electrical properties can be provided;
the values of n and m are respectively 1 to 200, and the value of p is 1 to 6, preferably 1 to 2.
The number average molecular weight of the curable polyphenyl ether resin is 1000-5000 g/mol; if the molecular weight is too small, the content of curable groups in the unit molecular weight is too large, and the brittleness of the cured product after crosslinking is large; if the molecular weight is too large, the solution viscosity of the polymer is large, the fluidity is poor, and the processing difficulty is increased.
The curable polyphenyl ether resin adopted by the invention has the advantages that not only is the end group provided with the curable group, but also the middle part of the molecular chain is provided with the crosslinkable curing group, a three-dimensional network structure is formed only when the molecular chain is crosslinked and cured under the action of heat, the middle part and the end part of the molecular chain can form crosslinking points, the number average molecular weight between the two crosslinking points is small, so that the crosslinked density of the cured material is high, the crosslinking degree is high, the glass transition temperature of the cured material is high, the heat resistance index such as the thermal decomposition temperature is high, and the cured material is possibly embrittled. Then, the present invention also adds a crosslinking agent that can promote the curing reaction. The function of the cross-linking agent is that unsaturated double bond groups in the cross-linking agent can react with curable groups in the curable polyphenyl ether, so that cross-linking and curing can be promoted, more cross-linking points are formed, the cross-linking density is high, and in order to change the brittleness of a cured product, the cross-linking agent containing flexible chains and unsaturated double bonds is also preferable to be added. Because the flexible chain exists in the cross-linking agent, the movable chain segments are arranged between the cross-linking points, when the cured product is acted by external force, the flexible chain segments between the cross-linking points can resist the damage of the external force through changing the conformation, and the toughness of the cured product is increased, so that the cross-linking density is high, the cross-linking degree is high, the toughness is also high, and the cross-linked cured product has the characteristic of a strong and tough polymer material.
The filler adopted by the invention mainly plays a role in reinforcement, and the shape, particle size, surface treatment method and filling amount of the filler have great influence on the reinforced material. The filler is generally in the shape of irregular particles, sheets, fibers, columns, spheres, hollow tubes or hollow microspheres, preferably in the shape of irregular particles, spheres or hollow microspheres, and the filler with a special shape such as spheres can obviously reduce the thermal expansion degree in the thickness direction of the board, namely in the Z-axis direction, when used in a copper-clad plate, can ensure the welding reliability of components on the printed circuit board, and if the expansion coefficient is large, the expansion degree of the welded components is inconsistent with the expansion of the board, the pins are broken by pulling, so that the functions of the components are invalid. Especially, if the thermal expansion of the substrate is large, under the condition that the expansion coefficients of the internal chip devices are inconsistent, the chips and devices packaged in the substrate are more easily damaged and fail. The more defects are generated in the reinforced material, the smaller the average particle size of the filler particles is, the more the filler particles are uniformly distributed in the material, the fewer the defects are, and the comprehensive performance of the material is good. The filler material is generally reinforced with a filler having a small average particle size. However, the filler with small average particle diameter has large surface energy, is easy to agglomerate and is easy to cause uneven distribution in the reinforcing material, and at the moment, the surface of the filler is required to be treated, so that the surface energy is reduced, and the filler is favorable for being uniformly dispersed in matrix resin.
The coupling agent adopted by the invention can carry out surface treatment on the filler, on one hand, the surface energy of the filler is reduced, the filler can not agglomerate, even if the filler agglomerates, the filler can be easily dispersed under the stirring and shearing actions, and on the other hand, the coupling agent plays the role of connecting the inorganic filler and the resin, improves the compatibility between the inorganic filler and the matrix resin, and enhances the binding force between the inorganic filler and the matrix resin. The special coupling agent not only plays the role, but also contains unsaturated double bonds, can react with matrix resin such as crosslinkable polyphenyl ether or crosslinking agent, and plays the dual roles of crosslinking and reinforcing the binding force of the filler. The special coupling agent containing unsaturated double bonds is mainly used in the invention, and is used for carrying out surface treatment on the filler and then being used in the composition and the preparation of the copper-clad plate.
In general, organic polymers have limiting oxygen indices of less than 28 and are combustible products. In order to be difficult to burn or ignite, the flame retardant is added into the polymer material or polymer composite material to achieve the effect of being difficult to burn or not burning. As a copper-clad plate material for special application, the flame retardance is a performance evaluation index, and the flame retardance grade reaches V0 grade of the American 94L standard or the equivalent grade of other standards. Halogen-containing flame retardant materials release dioxin and other harmful substances which seriously threaten human health and environment in the combustion or heating process. The flame retardant adopted by the invention is a halogen-free phosphorus-containing flame retardant, and the defects of the halogen-containing flame retardant material are avoided. In use, if the nitrogen flame retardant is compounded, the effect is better.
The rheological additive adopted by the invention can change the fluidity of the composition solution, is easy to coat or brush, and especially can prevent the phenomenon of sagging caused by flowing when the glue solution is coated too thick or the viscosity of the glue solution is small, thereby ensuring the uniformity of the coating thickness. The invention has the advantages that the filler amount is large, the fluidity is poor, the rheological additive is adopted, the fluidity of the glue solution in the preparation of the glue solution can be changed under the action of stirring shearing force, and meanwhile, the anti-sagging property is realized after the coating is finished.
As a preferable technical scheme:
the composition containing the curable polyphenyl ether comprises more than one crosslinking agent selected from dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, triallyl isocyanurate, divinylbenzene, styrene-butadiene copolymer with the number average molecular weight ranging from 500 g/mol to 3000g/mol, divinylbenzene homopolymer with the number average molecular weight ranging from 500 g/mol to 3000g/mol and polybutadiene with the number average molecular weight ranging from 500 g/mol to 3000 g/mol.
The preferable cross-linking agent molecules have a plurality of nonpolar double bonds, form a three-dimensional network structure through free radical addition reaction, achieve cross-linking and solidification, have no polar bonds or polar groups after the reaction, and can not increase the dielectric properties such as dielectric constant, dielectric loss and the like of the material.
The composition containing the curable polyphenyl ether comprises more than one of barium sulfate, talcum powder, calcium silicate, glass microspheres, hollow glass microspheres, silicon dioxide, aluminum oxide, titanium dioxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, magnesium hydroxide and polytetrafluoroethylene micro powder as filler;
when the filler is used, it is subjected to a baking treatment, and the following vinyl-containing coupling agent may be used for the surface treatment. The silane coupling agent containing vinyl is more than one of gamma-methacryloxypropyl trimethoxy silane, vinyl tri (2-methoxyethoxy) silane and vinyl triethoxy silane.
A filler of a curable polyphenylene ether-containing composition as described above, the filler having the shape of irregular particles, solid spheres or hollow microspheres, the filler having an average particle diameter D50 of less than 10 microns, preferably an average particle diameter D50 of less than 5 microns. The filler may also be in the shape of a sheet, a fiber, a column or a hollow tube.
The composition containing the curable polyphenyl ether, wherein the flame retardant is halogen-free phosphorus flame retardant, and specifically comprises the following components: triphenylphosphine oxide, p-xylyl bis-diphenylphosphinine oxide, bis (4-carboxyphenyl) phenylphosphine oxide, bis (3, 5-dimethylphenyl) phosphorus oxide, diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), 10- (2, 5-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (CAS: 107394-28-5) and 10- (2, 5-dihydroxy-4-phenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The composition containing the curable polyphenyl ether, and the rheological additive are more than one of acrylic ester, polysiloxane, fluorocarbon and polyether organic solvent.
The composition containing the curable polyphenyl ether comprises more than one of benzene, toluene, xylene, chloroform, 1,2 dichloroethane, trichloroethane, trichloroethylene, carbon tetrachloride, chlorobenzene, dichlorobenzene and butanone as solvent.
The invention also provides the application of the composition containing the curable polyphenyl ether, and the composition is firstly transferred to a gum dipping tank; then the substrate is completely immersed in a gum dipping tank, and the gum solution enters the substrate to finish the gum dipping process under the action of a gum dipping roller in the gum dipping tank; then extruding the impregnated matrix by a squeeze roller to ensure that the impregnation amount of the matrix is 40-70% (mass percent), and baking for 1-5 minutes at the temperature of 100-180 ℃ to obtain a prepreg;
The matrix is organic fiber fabric, organic fiber non-woven fabric, electronic grade glass fiber fabric or electronic grade glass fiber non-woven fabric.
The baking temperature and time are key factors in controlling prepreg fabrication. The baking temperature should be in the vicinity of the curing crosslinking point temperature of the composition, generally higher than the crosslinking point temperature, the solvent in the composition volatilizes in a short time, and the resin, crosslinking agent, etc. in the composition begin to crosslink and cure, but the time should not be too long. If the curing time is too long, the crosslinking degree is too high, the prepreg becomes brittle, and in the later stage of lamination, enough crosslinkable groups are not available, the adhesive force of the laminated copper-clad plate becomes poor, and the laminated copper-clad plate can be broken by a small stripping force, so that the use requirement is not met. Thus, both the baking temperature and the baking time are taken into account in this preparation process. The baking temperature determines the volatilization of the solvent in the composition and the onset of crosslinking of the curable material in the composition, and the baking time determines the dry state of the composition and the degree of crosslinking of the curable material in the composition, ensuring that sufficient curable groups are present in the subsequent step for bonding upon hot pressing, a process known as prepreg manufacture.
As a preferable technical scheme:
the application of the composition containing the curable polyphenyl ether comprises the steps of superposing a plurality of prepregs together, covering copper foil on one side or two sides of the superposed cured sheets, and pressing by a hot press to form a copper-clad plate with single-sided copper-clad or double-sided copper-clad;
the copper foil is an electrolytic copper foil or a rolled copper foil, and the surface roughness of the copper foil is less than 5 microns.
The application of the composition containing the curable polyphenyl ether has the advantages that the glass transition temperature of the copper-clad plate is 195-215 ℃, the 1% thermal weight loss temperature Td is 370-380 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 29-35 ppm/DEGC (refer to IPC-TM-650); the dielectric constant is 3.5-3.8 (refer to IPC-TM-650) at the frequency of 10GHz, and the dielectric loss is 0.00319-0.00370 (refer to IPC-TM-650); the ASTM-D5470 standard test heat conductivity is 0.7-1.0W/m.K, and the UL94 method test flame retardant rating is V0.
The unsaturated ethylenic group in the curable polyphenylene ether resin of the present invention is vinyl, propenyl, butenyl, butadienyl, pentenyl, prenyl, hexenyl, hexadienyl or cyclopentadienyl, preferably vinyl, propenyl or butenyl.
The thermosetting crosslinking temperature of the curable polyphenyl ether resin is low and is 150-160 ℃; at normal temperature, the solubility in benzene, toluene, dimethylbenzene and butanone solvents is large, the mass percentage of the solution concentration can reach 50-60 wt% at the maximum solubility, and the viscosity of the solution at the maximum solubility is 100-300 mPa.s; the curable polyphenylene ether resin has a hygroscopicity of not more than 0.05%, a dielectric constant (Dk) of 2.43 to 2.46 and a dielectric loss (Df) of 0.0007 to 0.0008 when measured at a frequency of 1 GHz.
Heat curing crosslinking temperature: and testing the relation between the dynamic viscosity and the temperature of the resin in a dynamic oscillation mode in an elastic deformation range by using a rheometer, wherein a temperature point corresponding to the time when the viscosity is suddenly increased from small to large on a viscosity-temperature change curve is the curing and crosslinking starting temperature point of the resin.
Hygroscopicity: astm d570-98;
Dk/Df：IPC-TM-650；
the preparation method of the curable polyphenyl ether resin comprises the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether (PPO-OH) in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reacting for a period of time, and adding p-bromophenol and CuCl/DMAP (catalyst, wherein DMAP represents p-dimethylaminopyridine) for reacting for 1-2 hours (when R in the curable polyphenyl ether resin) 3 、R 4 、R 5 And R is 6 This step is required when each is independently chosen from-H, otherwise no more p-bromophenol is required, i.e. corresponding to 0H; the purpose of the addition of p-bromophenol is to make the two ends of the double-end hydroxyl polyphenyl ether bear phenol groups, R 3 、R 4 、R 5 And R is 6 Precipitating with poor solvent of polyphenyl ether after the reaction of-H), and filtering and washing to obtain double-end hydroxyl polyphenyl ether (PPO-2 OH);
the phenolic compound is Or->Wherein R is 12 、R 13 、R 14 And R is 15 Each independently selected from-H, -CH 3 Or an unsaturated vinyl group having 2 to 8 carbon atoms, and R 12 、R 13 、R 14 And R is 15 At least one of which contains an unsaturated olefinic group;
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, precipitating with a poor solvent of the polyphenyl ether after the reaction is finished, and filtering and washing to obtain the curable polyphenyl ether resin;
end cappingThe agent is substance A and/or substance B; the structural formula of the substance A is as follows:the structural formula of the substance B is as follows: />Wherein R is 7 And R is 8 In ortho-, meta-or para-position of the benzene ring, R 9 And R is 10 In ortho-, meta-or para-position of the benzene ring, R 7 、R 8 、R 9 And R is 10 Each independently selected from-H, -CH 3 Or-ch=ch 2 A group, but R 7 And R is 8 Comprises at least one of-CH=CH 2 A group R 9 And R is 10 Comprises at least one of-CH=CH 2 A group; r is R 16 And R is 17 Each independently selected from-Cl, -Br-F, -I, -OH or-OCH 3 A group.
The invention adopts bisphenol containing different numbers of carbon-carbon unsaturated double bonds to react with single-end hydroxyl polyphenyl ether, redistribution reaction is carried out, simultaneously, bisphenol groups containing unsaturated double bonds are introduced into a molecular chain, namely, modification of side groups is carried out, and meanwhile, the molecular weight of the polyphenyl ether is regulated, so that double-end hydroxyl polyphenyl ether with smaller molecular weight, the side groups of which contain carbon-carbon unsaturated double bonds, can be obtained, the number of which can be designed, is reacted with a capping agent containing carbon-carbon unsaturated double bonds, capping is carried out, modification of the end groups of the molecular chain is completed, and finally, the crosslinkable and curable polyphenyl ether resin with moderate molecular weight and designable curing groups is obtained. According to the use requirement, the types and the number of the side groups and the end groups can be designed, and different dihydric phenols and end capping agents are adopted in the two-step reaction, so that the purposes of designable and adjustable types and numbers of the carbon-carbon double bond groups in the molecular chain of the curable polyphenyl ether resin are achieved. The cross-linking density of the cross-linked and solidified side group and end group can be effectively improved, so that the heat resistance of the solidified resin is good, the initial decomposition temperature is 395-403 ℃, the glass transition temperature is 150-173.9 ℃, the expansion coefficient is small, and the electrical property is superior to that of the thermoplastic polyphenyl ether resin.
The curable polyphenyl ether resin is characterized in that the middle part and the two end groups of the molecular chain contain olefinic groups, the addition reaction of free radicals can be respectively carried out under the action of heat or an initiator in processing application to form a three-dimensional network structure, the double bond content in the molecular chain of the curable polyphenyl ether resin can be regulated through the double bond contained in phenols or the double bond content in a blocking agent according to requirements, and further the controllable crosslinking degree, the designable material performance and the like can be realized.
In the prior art, the polyphenyl ether resin with the side group containing double bonds is obtained by C-O coupling polymerization under the oxidation condition of phenols with the side group not containing double bonds and phenols with the side group containing double bonds in the polymerization process, and the polyphenyl ether resin is a gradual polymerization mechanism. The phenolic monomers in the molecular chain are random and random, so that the distribution of the side group double bonds in the polyphenyl ether macromolecular chain is irregular, and the content of the side group double bonds is not accurately controllable. Based on the side group modified polyphenyl ether resin, epoxy groups are introduced into the end groups or acrylate groups are introduced into the end groups to obtain the curable polyphenyl ether. The two methods are carried out by using phenols containing double bonds during polymerization, introducing vinyl groups into the middle part of the molecular chain of the polyphenyl ether resin, which is difficult to realize in practical operation, because in practice, the number of the phenol groups containing double bonds polymerized into the molecular chain and the distribution in the molecular chain are uncontrollable, and in the next step of end group modification, the modifier reacts with the unknown number of side vinyl groups easily to form gel, so that the modification of the end groups of the polyphenyl ether molecular chain fails.
The invention utilizes a two-step reaction, firstly prepares double-end hydroxyl polyphenyl ether (PPO-2 OH) containing alkene groups in the middle part of a molecular chain, and the number of double bonds is accurately controllable through phenols; and secondly, reacting the end-OH group of the double-end hydroxyl polyphenyl ether (PPO-2 OH) with a blocking agent under the mild reaction condition and the action of a catalyst, and connecting the vinyl group into the molecular chain, so that the reaction of a carbon-carbon double bond in the blocking agent and the vinyl group in the middle part of the molecular chain of the double-end hydroxyl polyphenyl ether caused by the violent reaction condition is avoided, and finally, the curable polyphenyl ether resin with the vinyl groups in the middle part of the molecular chain and at the two end ends can be prepared.
Advantageous effects
(1) The composition containing the curable polyphenyl ether resin has the advantages that the side group and the two end groups of the molecular structure of the curable polyphenyl ether resin are provided with the curable functional groups, and the content of the curable functional groups in the unit molecular weight is high; the functional group is nonpolar unsaturated carbon-carbon double bond, the activity is high, the reaction temperature is low, and the conditions of crosslinking and curing are mild;
(2) The curable high-crosslinking-degree polyphenyl ether resin has the advantages of small molecular weight, good solubility, moderate solution viscosity, good solution fluidity, capability of preparing a solution with high solid content and excellent processability, and is particularly suitable for preparing a solution;
(3) The composition containing the curable polyphenyl ether resin provided by the invention has the advantages that a plurality of crosslinking points are formed after curing, the crosslinking density is high, and the heat resistance is good. Meanwhile, the composition has the characteristics of high crosslinking density, high crosslinking degree, high toughness and strong and tough polymer material due to the selection of the crosslinking agent containing the flexible chain;
(4) According to the application of the composition containing the curable polyphenyl ether resin, the preferable particle form of the filler and the treatment mode of the coupling agent enhance the binding force between the filler and the resin, the heat conductivity is good, and the thermal expansion coefficients of the copper-clad plate in the thickness direction before and after the Tg temperature are obviously reduced;
(5) The application of the composition containing the curable polyphenyl ether resin has the characteristics of low dielectric constant, low dielectric loss, high crosslinking degree, high heat resistance, small expansion coefficient and good heat conductivity, and the glass transition temperature of the prepared copper-clad plate is 195-215 ℃, the 1% thermal weight loss temperature Td is 370-380 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 29-35 ppm/DEGC; the dielectric constant is 3.5-3.8 under the frequency of 10GHz, and the dielectric loss is 0.00319-0.00370; the ASTM-D5470 standard test heat conductivity coefficient is 0.7-1.0W/m.K, the UL94 method test flame retardant rating is V0, and the method is particularly suitable for preparing high-speed circuit substrates.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
TABLE 1 structural formula of phenolic compounds
TABLE 2 Structure of blocking agent
/>
The single-end hydroxyl polyphenyl ether disclosed by the application has the following sources: obtained by an oxidative coupling method according to a gradual polymerization mechanism; commercial products such as PPO Resin630, PPO Resin640, PPO Resin646 of the salet industries (SABIC).
Example 1
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 3 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X1 in Table 1 | 0.1 part by weight |
| Solvent(s) | Benzene | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 50 parts by weight |
| Initiator(s) | Dicumyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | Hydroquinone (HQ) | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 5 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A1 in Table 2 | 3 parts by weight |
| Solvent(s) | Benzene | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 50 parts by weight |
| Polymerization inhibitor | Hydroquinone (HQ) | 0.001 part by weight |
| Catalyst | Potassium carbonate | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 151.1℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.44 and Df is 0.0007.
Example 2
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 3 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X2 in Table 1 | 0.1 part by weight |
| Solvent(s) | Toluene (toluene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 60 parts by weight |
| Initiator(s) | Dibenzoyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | Para-hydroxyanisole | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 4 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A2 in Table 2 | 3 parts by weight |
| Solvent(s) | Toluene (toluene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 60 parts by weight |
| Polymerization inhibitor | Para-hydroxyanisole | 0.001 part by weight |
| Catalyst | Cesium carbonate | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 150.8℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 3
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 80 ℃, and the reaction time is 2 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin640 | 1 part by weight |
| Phenolic compounds | X3 in Table 1 | 0.1 part by weight |
| Solvent(s) | Xylene (P) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 70 parts by weight |
| Initiator(s) | Tert-butyl peroxybenzoate | 0.05 part by weight |
| Polymerization inhibitor | 2-tert-butylhydroquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 20 ℃, and the reaction time is 5 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A3 in table 2 | 3 parts by weight |
| Solvent(s) | Xylene (P) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 70 parts by weight |
| Polymerization inhibitor | 2-tert-butylhydroquinone | 0.001 part by weight |
| Catalyst | Sodium hydroxide | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 152.0℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 4
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 50 ℃, and the reaction time is 3 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X4 in Table 1 | 0.1 part by weight |
| Solvent(s) | Trichloromethane | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol and water in a volume ratio of 1:10 | 80 parts by weight |
| Initiator(s) | Diisopropyl peroxydicarbonate | 0.05 part by weight |
| Polymerization inhibitor | 2, 5-Di-tert-butylhydroquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 40 ℃, and the reaction time is 2 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B1 in Table 2 | 2 parts by weight |
| Solvent(s) | Trichloromethane | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol and water in a volume ratio of 1:10 | 80 parts by weight |
| Polymerization inhibitor | 2, 5-Di-tert-butylhydroquinone | 0.001 part by weight |
| Catalyst | Pyridine compound | 1 part by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 158.5℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 5
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 10 ℃, and the reaction time is 10 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| Type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X5 in Table 1 | 0.1 part by weight |
| Solvent(s) | 1,2 dichloroethane | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 90 parts by weight |
| Initiator(s) | Di-tert-butyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | P-benzoquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is minus 30 ℃, and the reaction time is 5 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 154.3℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk was 2.43 and Df was 0.0007.
Example 6
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 10 ℃, and the reaction time is 10 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| Type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X6 in Table 1 | 0.1 part by weight |
| Solvent(s) | Trichloroethane (Trichloroethane) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 100 parts by weight of |
| Initiator(s) | Tert-butyl peroxypivalate | 0.05 part by weight |
| Polymerization inhibitor | Methyl hydroquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 0 ℃, and the reaction time is 4 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A6 in Table 2 | 3 parts by weight |
| Solvent(s) | Trichloroethane (Trichloroethane) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 100 parts by weight of |
| Polymerization inhibitor | Methyl hydroquinone | 0.001 part by weight |
| Catalyst | Mixture of dodecyl trimethyl ammonium chloride and potassium carbonate in mass ratio of 1:1 | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 152.2℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 7
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 10 ℃, and the reaction time is 10 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin640 | 1 part by weight |
| Phenolic compounds | X7 in Table 1 | 0.1 part by weight |
| Solvent(s) | Trichloroethylene (trichloroethylene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 50 parts by weight |
| Initiator(s) | Lauroyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | Tetrachlorobenzoquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 40 ℃, and the reaction time is 3 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B1 in Table 2 | 2 parts by weight |
| Solvent(s) | Trichloroethylene (trichloroethylene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 50 parts by weight |
| Polymerization inhibitor | Tetrachlorobenzoquinone | 0.001 part by weight |
| Catalyst | Pyridine compound | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 157.3 ℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 8
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 40 ℃, and the reaction time is 9 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
/>
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 2 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B2 in Table 2 | 2 parts by weight |
| Solvent(s) | Carbon tetrachloride | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 60 parts by weight |
| Polymerization inhibitor | Ferric chloride | 0.001 part by weight |
| Catalyst | Picoline | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 156.2℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 9
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 40 ℃, and the reaction time is 8 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin640 | 1 part by weight |
| Phenolic compounds | X9 in Table 1 | 0.1 part by weight |
| Solvent(s) | Chlorobenzene (Chlorobenzene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 70 parts by weight |
| Initiator(s) | 1, 4-paraphenylene diamineQuinone | 0.05 part by weight |
| Polymerization inhibitor | Cuprous chloride | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 2 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B3 in Table 2 | 2 parts by weight |
| Solvent(s) | Chlorobenzene (Chlorobenzene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 70 parts by weight |
| Polymerization inhibitor | Cuprous chloride | 0.001 part by weight |
| Catalyst | Triethylamine | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 155.1℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 10
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 40 ℃, and the reaction time is 8 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B4 in Table 2 | 2 parts by weight |
| Solvent(s) | Dichlorobenzene (dichlorobenzene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 80 parts by weight |
| Polymerization inhibitor | Copper sulfate | 0.001 part by weight |
| Catalyst | Diisopropylethylamine | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 151.6℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk was 2.43 and Df was 0.0007.
Example 11
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 50 ℃, and the reaction time is 7 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| Type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin646 | 1 part by weight |
| Phenolic compounds | X11 in Table 1 | 0.1 part by weight |
| Solvent(s) | Nitrobenzene | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 90 parts by weight |
| Initiator(s) | Dicumyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | Hydroquinone (HQ) | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 80 ℃, and the reaction time is 1h; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B5 in Table 2 | 2 parts by weight |
| Solvent(s) | Nitrobenzene | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 90 parts by weight |
| Polymerization inhibitor | Hydroquinone (HQ) | 0.001 part by weight |
| Catalyst | Pyridine compound | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 152.4℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 12
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 6 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is-20 ℃ and the reaction time is 5 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B6 in Table 2 | 2 parts by weight |
| Solvent(s) | Butanone | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 100 parts by weight of |
| Polymerization inhibitor | Para-hydroxy benzeneMethyl ether | 0.001 part by weight |
| Catalyst | Picoline | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 153.1℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 13a
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 6 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X13 in Table 1 | 0.1 part by weight |
| Solvent(s) | Benzene | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 50 parts by weight |
| Initiator(s) | Dibenzoyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | 2-tert-butylhydroquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is-10 ℃, and the reaction time is 4 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B7 in Table 2 | 2 parts by weight |
| Solvent(s) | Benzene | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 50 parts by weight |
| Polymerization inhibitor | 2-tert-butylhydroquinone | 0.001 part by weight |
| Catalyst | Sulfuric acid | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 152.4℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.44 and Df is 0.0007.
Example 13b
A method for producing a curable polyphenylene ether resin, which is substantially the same as in example 13a except that the catalyst in step (2) in example 13a is replaced with dicyclohexylcarbodiimide and the remaining conditions are the same, the resulting curable polyphenylene ether resin has a heat-curing crosslinking temperature of 152.6℃and a hygroscopicity of 0.05%, and is tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 13c
A process for preparing a curable polyphenylene ether resin, which is substantially the same as in example 13a except that the catalyst in step (2) in example 13a is replaced with 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, and the remaining conditions are the same, the resulting curable polyphenylene ether resin has a heat curing crosslinking temperature of 152.1℃and a hygroscopicity of 0.05%, and is measured at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 14a
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 5 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin646 | 1 part by weight |
| Phenolic compounds | X14 in Table 1 | 0.1 part by weight |
| Solvent(s) | Toluene (toluene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 80 parts by weight |
| Initiator(s) | Lauroyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | 2, 5-Di-tert-butylhydroquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 20 ℃, and the reaction time is 3 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B8 in Table 2 | 2 parts by weight |
| Solvent(s) | Toluene (toluene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 80 parts by weight |
| Polymerization inhibitor | 2, 5-Di-tert-butylhydroquinone | 0.001 part by weight |
| Catalyst | Polyphosphoric acid | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 153.4℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 14b
A method for producing a curable polyphenylene ether resin, which is substantially the same as in example 14a except that the catalyst in step (2) in example 14a is replaced with diisopropylcarbodiimide and the remaining conditions are the same, the curable polyphenylene ether resin produced has a thermosetting crosslinking temperature of 153.2 ℃ and a hygroscopicity of 0.05%, and is tested at a frequency of 1 GHz: dk was 2.43 and Df was 0.0007.
Example 15
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 4 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| Type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X15 in Table 1 | 0.1 part by weight |
| Solvent(s) | Xylene (P) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 100 parts by weight of |
| Initiator(s) | Tert-butyl peroxybenzoate | 0.05 part by weight |
| Polymerization inhibitor | P-benzoquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 50 ℃, and the reaction time is 3 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B9 in Table 2 | 2 parts by weight |
| Solvent(s) | Xylene (P) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 100 parts by weight of |
| Polymerization inhibitor | P-benzoquinone | 0.001 part by weight |
| Catalyst | Potassium hydroxide | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 152.8℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 16
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 70 ℃, and the reaction time is 4 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X16 in Table 1 | 0.1 part by weight |
| Solvent(s) | Trichloromethane | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 50 parts by weight |
| Initiator(s) | Tert-butyl peroxypivalate | 0.05 part by weight |
| Polymerization inhibitor | Methyl hydroquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 80 ℃, and the reaction time is 1h; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B10 in Table 2 | 2 parts by weight |
| Solvent(s) | Trichloromethane | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 50 parts by weight |
| Polymerization inhibitor | Methyl hydroquinone | 0.001 part by weight |
| Catalyst | Sulfuric acid | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 153.1℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 17
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 70 ℃, and the reaction time is 3 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin646 | 1 part by weight |
| Phenolic compounds | X17 in Table 1 | 0.1 part by weight |
| Solvent(s) | 1,2 dichloroethane | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 60 parts by weight |
| Initiator(s) | Diisopropyl peroxydicarbonate | 0.05 part by weight |
| Polymerization inhibitor | Tetrachlorobenzoquinone | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 3 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A1 in Table 2 | 3 parts by weight |
| Solvent(s) | 1,2 dichloroethane | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 60 parts by weight |
| Polymerization inhibitor | Tetrachlorobenzoquinone | 0.001 part by weight |
| Catalyst | Cesium carbonate and potassium iodide mixture in a mass ratio of 1:1 | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 151.8℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 18a
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin646 | 1 part by weight |
| Phenolic compounds | X18 in Table 1 | 0.1 part by weight |
| Solvent(s) | Trichloroethane (Trichloroethane) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 70 parts by weight |
| Initiator(s) | Dicyclohexyl peroxydicarbonate | 0.05 part by weight |
| Polymerization inhibitor | Ferric chloride | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 70 ℃, and the reaction time is 1h; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 151.0℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 18b
A method for producing a curable polyphenylene ether resin, which is substantially the same as in example 18a, except that the catalyst in step (2) in example 18a is replaced with a mixture of tetradecyltrimethylammonium chloride and potassium carbonate in a mass ratio of 1:1, and the remaining conditions are the same, the resulting curable polyphenylene ether resin has a heat curing crosslinking temperature of 151.2℃and a hygroscopicity of 0.05%, and is measured at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 18c
A method for producing a curable polyphenylene ether resin, which is substantially the same as in example 18a, except that the catalyst in step (2) in example 18a is replaced with a mixture of tetrabutylammonium bisulfate and sodium hydroxide in a mass ratio of 1:1, and the remaining conditions are the same, the resulting curable polyphenylene ether resin has a heat-curing crosslinking temperature of 151.4 ℃and a hygroscopicity of 0.05%, and is tested at a frequency of 1 GHz: dk is 2.45 and Df is 0.0007.
Example 19
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 80 ℃, and the reaction time is 2 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin646 | 1 part by weight |
| Phenolic compounds | X12 in Table 1 | 0.1 part by weight |
| Solvent(s) | Trichloroethylene (trichloroethylene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 100 parts by weight of |
| Initiator(s) | 1, 4-terephthalquinone | 0.05 part by weight |
| Polymerization inhibitor | Cuprous chloride | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 10 ℃, and the reaction time is 3 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A3 in table 2 | 3 parts by weight |
| Solvent(s) | Trichloroethylene (trichloroethylene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 100 parts by weight of |
| Polymerization inhibitor | Cuprous chloride | 0.001 part by weight |
| Catalyst | Mixture of tetrabutylammonium bromide and potassium carbonate in a mass ratio of 1:1 | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 152.3℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 20
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 90 ℃, and the reaction time is 2 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin630 | 1 part by weight |
| Phenolic compounds | X3 in Table 1 | 0.1 part by weight |
| Solvent(s) | Carbon tetrachloride | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 70 parts by weight |
| Initiator(s) | 3, 5-tetramethyl biphenyl diquinone | 0.05 part by weight |
| Polymerization inhibitor | Copper sulfate | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 80 ℃, and the reaction time is 1h; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A4 in table 2 | 3 parts by weight |
| Solvent(s) | Carbon tetrachloride | 5 parts by weight |
| Poor solvent for polyphenylene ether | Ethanol | 70 parts by weight |
| Polymerization inhibitor | Copper sulfate | 0.001 part by weight |
| Catalyst | Mixture of tetrabutylammonium chloride and cesium carbonate in a mass ratio of 1:1 | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 153.1℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 21
A method for preparing a curable polyphenylene ether resin, comprising the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 100 ℃, and the reaction time is 2 hours; precipitating with a poor solvent of polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
| Type of material in step (1) | Material name | Usage amount |
| Single-end hydroxyl polyphenyl ether | PPO*Resin640 | 1 part by weight |
| Phenolic compounds | X4 in Table 1 | 0.1 part by weight |
| Solvent(s) | Chlorobenzene (Chlorobenzene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 80 parts by weight |
| Initiator(s) | Dicumyl peroxide | 0.05 part by weight |
| Polymerization inhibitor | Hydroquinone (HQ) | 0.001 part by weight |
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 90 ℃, and the reaction time is 1h; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A5 in Table 2 | 3 parts by weight |
| Solvent(s) | Chlorobenzene (Chlorobenzene) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 80 parts by weight |
| Polymerization inhibitor | Hydroquinone (HQ) | 0.001 part by weight |
| Catalyst | Potassium hydroxide | 2 parts by weight |
The resulting curable polyphenylene ether resin had a heat curing crosslinking temperature of 150.3℃and a hygroscopicity of 0.05% and was tested at a frequency of 1 GHz: dk is 2.46 and Df is 0.0007.
Example 22
A method for preparing a curable polyphenylene ether resin, the same as in step (1) of example 1, the second step being as follows:
Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 30 ℃, and the reaction time is 5 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | A1 and A6 in Table 2 | 1.5 parts by weight each |
| Solvent(s) | Benzene | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 50 parts by weight |
| Polymerization inhibitor | Hydroquinone (HQ) | 0.001 part by weight |
| Catalyst | Potassium carbonate | 2 parts by weight |
The thermosetting crosslinking temperature of the prepared curable polyphenyl ether resin is 150.6 ℃; the moisture absorption of the curable polyphenylene ether resin was 0.05%, dk at 1GHz of the curable polyphenylene ether resin was 2.44, and Df was 0.0007.
Example 23
A method for preparing a curable polyphenylene ether resin, the same as in step (1) of example 15, the second step being as follows:
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, wherein the reaction temperature is 50 ℃, and the reaction time is 3 hours; and after the reaction is finished, precipitating by using a poor solvent of the polyphenyl ether, and filtering and washing to obtain the curable polyphenyl ether resin.
| Type of material in step (2) | Material name | Usage amount |
| Double-end hydroxyl polyphenyl ether | The preparation method comprises the following step (1) | 1 part by weight |
| End capping agent | B3 and B5 in Table 2 | 1 part by weight each |
| Solvent(s) | Xylene (P) | 5 parts by weight |
| Poor solvent for polyphenylene ether | Methanol | 100 parts by weight of |
| Polymerization inhibitor | P-benzoquinone | 0.001 part by weight |
| Catalyst | Potassium hydroxide | 2 parts by weight |
The thermosetting crosslinking temperature of the prepared curable polyphenyl ether resin is 150.7 ℃; the moisture absorption of the curable polyphenylene ether resin was 0.05%, dk at 1GHz of the curable polyphenylene ether resin was 2.45, and Df was 0.0007.
Example 24
A preparation method of a curable polyphenyl ether resin is basically the same as that of the embodiment 1, except that in the step (1), p-bromophenol and a catalyst CuCl/DMAP are added before the reaction is finished, the reaction is carried out for 2 hours, and then the double-end hydroxyl polyphenyl ether is obtained after precipitation, filtration and washing according to the same method;
the thermosetting crosslinking temperature of the prepared curable polyphenyl ether resin is 152 ℃; the moisture absorption of the curable polyphenylene ether resin was 0.051, dk at 1GHz of the curable polyphenylene ether resin was 2.45, and Df was 0.0007.
The molecular chain structure of the curable polyphenylene ether in one of the curable polyphenylene ether resins produced in examples 1 to 24 described above satisfies the following design:
Wherein R is 1 And R is 2 Each independently selected from formula I or formula II; r is R 3 、R 4 、R 5 And R is 6 Each independently selected from-H or-CH 3 The method comprises the steps of carrying out a first treatment on the surface of the X is of the structure Or->Wherein R is 12 、R 13 、R 14 And R is 15 Each independently selected from-H, -CH 3 Or an unsaturated vinyl group having 2 to 8 carbon atoms, and R 12 、R 13 、R 14 And R is 15 At least one of which contains an unsaturated olefinic group;
the structural formula I is:
the structural formula II is as follows:
wherein R is 7 And R is 8 In ortho-, meta-or para-position of the benzene ring, R 9 And R is 10 In ortho-, meta-or para-position of the benzene ring, R 7 、R 8 、R 9 And R is 10 Each independently selected from-H, -CH 3 Or-ch=ch 2 A group, and R 7 And R is 8 Comprises at least one of-CH=CH 2 A group R 9 And R is 10 Comprises at least one of-CH=CH 2 A group;
the value ranges of n and m are respectively 1-200, and the value range of p is 1-6;
the number average molecular weight of the curable polyphenyl ether resin prepared by the invention is 1000-5000 g/mol. At normal temperature, the solubility in benzene, toluene, xylene and butanone solvents is large, the mass percentage of the solution concentration can reach 50-60 wt% at the maximum solubility, and the viscosity of the solution at the maximum solubility is 100-300 mPa.s.
Example 25
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
Transferring the composition containing the curable polyphenyl ether to a dipping tank; then fully immersing the aramid fiber cloth into a gum dipping tank, and under the action of a gum dipping roller in the gum dipping tank, enabling the gum solution to enter the matrix to finish the gum dipping process; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 65%, and baking for 2 minutes at 160 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering a copper foil (electrolytic copper foil with the surface roughness of 4 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
the glass transition temperature of the prepared copper-clad plate is 198 ℃, the 1% thermal weight loss temperature Td is 375 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 33 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.72 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 26
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing the ultra-high molecular weight polyethylene fiber cloth into a gum dipping tank, and enabling the gum solution to enter the inside of the matrix to finish the gum dipping process under the action of a gum dipping roller in the gum dipping tank; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 56%, and baking for 4 minutes at the temperature of 150 ℃ to obtain a prepreg;
Laminating 6 prepregs together, covering a copper foil (rolled copper foil with the surface roughness of 4 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
the glass transition temperature of the prepared copper-clad plate is 195 ℃, the 1% thermal weight loss temperature Td is 371 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 34 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.65 and the dielectric loss is 0.0033; the ASTM-D5470 standard test has a thermal conductivity of 0.9W/mK and the UL94 method test has a flame retardant rating of V0.
Example 27
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing the polyether-ether-ketone fiber cloth into a gum dipping tank, and enabling the gum solution to enter the inside of a matrix to finish the gum dipping process under the action of a gum dipping roller in the gum dipping tank; then extruding the impregnated matrix by a squeeze roller to enable the impregnation amount of the matrix to be 52%, and baking for 3 minutes at 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering a copper foil (rolled copper foil with surface roughness of 3 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
The glass transition temperature of the prepared copper-clad plate is 198 ℃, the 1% thermal weight loss temperature Td is 374 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 29 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.73 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.9W/mK and the UL94 method test has a flame retardant rating of V0.
Example 28
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 1078 electronic grade glass cloth in a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 48%, and baking for 5 minutes at the temperature of 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering a copper foil (rolled copper foil with surface roughness of 3 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
the glass transition temperature of the prepared copper-clad plate is 210 ℃, the 1% thermal weight loss temperature Td is 378 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 30 ppm/DEG C; a test dielectric constant of 3.76 at a frequency of 10GHz and a dielectric loss of 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 29
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 58%, and baking for 5 minutes at the temperature of 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering a copper foil (electrolytic copper foil with the surface roughness of 4 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
the glass transition temperature of the prepared copper-clad plate is 210 ℃, the 1% thermal weight loss temperature Td is 377 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 31 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.75 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 30
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix by a squeeze roller to enable the impregnation amount of the matrix to be 52%, and baking for 5 minutes at 150 ℃ to obtain a prepreg;
Laminating 6 prepregs together, covering a copper foil (electrolytic copper foil with the surface roughness of 4 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
the glass transition temperature of the prepared copper-clad plate is 213 ℃, the 1% thermal weight loss temperature Td is 378 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 31 ppm/DEG C; a test dielectric constant of 3.76 at a frequency of 10GHz and a dielectric loss of 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.9W/mK and the UL94 method test has a flame retardant rating of V0.
Example 31
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix by a squeeze roller to enable the impregnation amount of the matrix to be 52%, and baking for 5 minutes at 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering a copper foil (electrolytic copper foil with the surface roughness of 4 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
The glass transition temperature of the prepared copper-clad plate is 215 ℃, the 1% thermal weight loss temperature Td is 380 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 30 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.74 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.9W/mK and the UL94 method test has a flame retardant rating of V0.
Example 32
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 47%, and baking for 5 minutes at the temperature of 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering a copper foil (electrolytic copper foil with the surface roughness of 4 microns) on one side of the laminated cured sheet, and pressing by a hot press to form a copper-clad plate with single-sided copper;
the glass transition temperature of the prepared copper-clad plate is 211 ℃, the 1% thermal weight loss temperature Td is 378 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 31 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.75 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 33
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 62%, and baking for 5 minutes at the temperature of 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering copper foil (electrolytic copper foil with surface roughness of 4 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
the glass transition temperature of the prepared copper-clad plate is 213 ℃, the 1% thermal weight loss temperature Td is 378 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 31 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.75 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 34
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix by a squeeze roller to enable the impregnation amount of the matrix to be 52%, and baking for 5 minutes at 150 ℃ to obtain a prepreg;
Laminating 6 prepregs together, covering copper foil (electrolytic copper foil with surface roughness of 4 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
the glass transition temperature of the prepared copper-clad plate is 215 ℃, the 1% thermal weight loss temperature Td is 379 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 31 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.75 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 1W/mK and the UL94 method test has a flame retardant rating of V0.
Example 35
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 60%, and baking for 4 minutes at the temperature of 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering copper foil (rolled copper foil with surface roughness of 3 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
The glass transition temperature of the prepared copper-clad plate is 210 ℃, the 1% thermal weight loss temperature Td is 375 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 32 ppm/DEG C; a test dielectric constant of 3.76 at a frequency of 10GHz and a dielectric loss of 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 36
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix by a squeeze roller to enable the impregnation amount of the matrix to be 42%, and baking for 3 minutes at 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering copper foil (rolled copper foil with surface roughness of 3 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
the glass transition temperature of the prepared copper-clad plate is 211 ℃, the 1% thermal weight loss temperature Td is 376 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 32 ppm/DEG C; a test dielectric constant of 3.76 at a frequency of 10GHz and a dielectric loss of 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.9W/mK and the UL94 method test has a flame retardant rating of V0.
Example 37
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 46%, and baking for 3 minutes at the temperature of 150 ℃ to obtain a prepreg;
laminating 6 prepregs together, covering copper foil (rolled copper foil with surface roughness of 3 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
the glass transition temperature of the prepared copper-clad plate is 210 ℃, the 1% thermal weight loss temperature Td is 377 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 32 ppm/DEG C; a test dielectric constant of 3.76 at a frequency of 10GHz and a dielectric loss of 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.9W/mK and the UL94 method test has a flame retardant rating of V0.
Example 38
A composition containing curable polyphenyl ether comprises the following components in parts by weight:
transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing 2116 electronic grade glass cloth into a dipping tank, and entering glue solution into a matrix to finish the dipping process under the action of a dipping roller in the dipping tank; then extruding the impregnated matrix by a squeeze roller to ensure that the impregnation amount of the matrix is 53%, and baking for 3 minutes at 150 ℃ to obtain a prepreg;
Laminating 6 prepregs together, covering copper foil (rolled copper foil with surface roughness of 3 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
the glass transition temperature of the prepared copper-clad plate is 210 ℃, the 1% thermal weight loss temperature Td is 376 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 32 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.73 and the dielectric loss is 0.0032; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 39
A composition comprising a curable polyphenylene ether, each of which is substantially the same as in example 25 except that the curable polyphenylene ether resin is selected from the curable polyphenylene ether resins produced in example 13c and does not contain a crosslinking agent.
Transferring the composition containing the curable polyphenyl ether to a dipping tank; then fully immersing the aramid fiber cloth into a gum dipping tank, and under the action of a gum dipping roller in the gum dipping tank, enabling the gum solution to enter the matrix to finish the gum dipping process; then extruding the impregnated matrix through an extrusion roller to enable the impregnation amount of the matrix to be 54%, and baking for 3 minutes at 153 ℃ to obtain a prepreg;
Laminating 6 prepregs together, covering copper foil (rolled copper foil with surface roughness of 3 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
the glass transition temperature of the prepared copper-clad plate is 198 ℃, the 1% thermal weight loss temperature Td is 376 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 32 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.75 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.8W/mK and the UL94 method test has a flame retardant rating of V0.
Example 40
A composition comprising a curable polyphenylene ether, each of which is substantially the same as in example 26 except that the curable polyphenylene ether resin was selected from the curable polyphenylene ether resins produced in example 14a, and did not contain a crosslinking agent and a silane coupling agent.
Transferring the composition containing the curable polyphenyl ether to a dipping tank; completely immersing the ultra-high molecular weight polyethylene fiber cloth into a gum dipping tank, and enabling the gum solution to enter the inside of the matrix to finish the gum dipping process under the action of a gum dipping roller in the gum dipping tank; then extruding the impregnated matrix by a squeeze roller to ensure that the impregnation amount of the matrix is 63%, and baking for 3 minutes at the temperature of 154 ℃ to obtain a prepreg;
Laminating 6 prepregs together, covering copper foil (rolled copper foil with surface roughness of 3 microns) on two sides of the laminated cured sheet, and pressing by a hot press to form a double-sided copper-clad plate;
the glass transition temperature of the prepared copper-clad plate is 200 ℃, the 1% thermal weight loss temperature Td is 376 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 32 ppm/DEG C; the test dielectric constant at 10GHz frequency is 3.75 and the dielectric loss is 0.0037; the ASTM-D5470 standard test has a thermal conductivity of 0.9W/mK and the UL94 method test has a flame retardant rating of V0.
Examples 41 to 53
A composition containing a curable polyphenylene ether, each of which was substantially the same as in example 28 except that the curable polyphenylene ether resin was selected from the curable polyphenylene ether resins produced in Table 4.
The composition was applied to the substrate (2116 electronic grade glass cloth) in example 28, the application parameters are shown in Table 4, and the performance index of the obtained copper-clad plate is shown in Table 5.
TABLE 4 Table 4
TABLE 5
/>
Claims (10)
1. A composition containing curable polyphenyl ether is characterized by comprising the following components in parts by weight:
curable polyphenylene ether resin: 100 parts;
crosslinking agent: 0-10 parts;
and (3) filling: 30-70 parts;
vinyl-containing silane coupling agent: 0-1 part;
Flame retardant: 1-20 parts;
rheology aid: 0.1-5 parts;
solvent: 50-100 parts;
in the composition, the molecules of the curable polyphenylene ether resin have the following structure:
wherein R is 1 And R is 2 Each independently selected from formula I or formula II; r is R 3 、R 4 、R 5 And R is 6 is-H; x is of the structure Or->Wherein R is 12 、R 13 、R 14 And R is 15 Each independently selected from-H, -CH 3 Or an unsaturated vinyl group having 2 to 8 carbon atoms, and R 12 、R 13 、R 14 And R is 15 At least one of which contains an unsaturated olefinic group;
the structural formula I is:
the structural formula II is as follows:
wherein R is 7 And R is 8 In ortho-, meta-or para-position of the benzene ring, R 9 And R is 10 In ortho-, meta-or para-position of the benzene ring, R 7 、R 8 、R 9 And R is 10 Each independently selected from-H, -CH 3 Or-ch=ch 2 A group, and R 7 And R is 8 Comprises at least one of-CH=CH 2 A group R 9 And R is 10 Comprises at least one of-CH=CH 2 A group;
the value ranges of n and m are respectively 1-200, and the value range of p is 1-6;
the number average molecular weight of the curable polyphenyl ether resin is 1000-5000 g/mol;
the preparation method of the curable polyphenyl ether resin comprises the following steps:
(1) Stirring and dissolving single-end hydroxyl polyphenyl ether in a solvent, keeping stirring, adding an initiator, a phenolic compound and a polymerization inhibitor into the solution for reaction for a period of time, adding p-bromophenol and CuCl/DMAP for reaction for 1-2 hours, precipitating with a poor solvent of the polyphenyl ether after the reaction is finished, and filtering and washing to obtain double-end hydroxyl polyphenyl ether;
The phenolic compound is Or->
(2) Stirring and dissolving the double-end hydroxyl polyphenyl ether obtained in the step (1) in a solvent, keeping stirring, adding a blocking agent, a catalyst and a polymerization inhibitor into the solution for reaction, precipitating with a poor solvent of the polyphenyl ether after the reaction is finished, and filtering and washing to obtain the curable polyphenyl ether resin;
the end capping agent is substance A and/or substance B; the structural formula of the substance A is as follows:the structural formula of the substance B is as follows: />Wherein R is 16 And R is 17 Each independently selected from-Cl, -Br-F, -I, -OH or-OCH 3 A group.
2. The curable polyphenylene ether-containing composition according to claim 1, wherein the crosslinking agent is one or more of dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyvalerate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, triallyl isocyanurate, divinylbenzene, styrene-butadiene copolymer having a number average molecular weight in the range of 500 to 3000g/mol, divinylbenzene homopolymer having a number average molecular weight in the range of 500 to 3000g/mol, and polybutadiene having a number average molecular weight in the range of 500 to 3000 g/mol.
3. The composition of claim 1, wherein the filler is one or more of barium sulfate, talc, calcium silicate, glass microspheres, silica, aluminum oxide, titanium dioxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, magnesium hydroxide, and polytetrafluoroethylene micropowder;
the silane coupling agent containing vinyl is more than one of gamma-methacryloxypropyl trimethoxy silane, vinyl tri (2-methoxyethoxy) silane and vinyl triethoxy silane.
4. A curable polyphenylene ether-containing composition according to claim 3, wherein the filler has an average particle size D50 of less than 10 microns.
5. The curable polyphenylene ether-containing composition according to claim 1, wherein the flame retardant is one or more of triphenylphosphine oxide, p-xylyl bis-diphenylphosphino oxide, bis (4-carboxyphenyl) phenylphosphine oxide, bis (3, 5-dimethylphenyl) phosphine oxide, diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphine, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10- (2, 5-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.
6. The curable polyphenylene ether-containing composition according to claim 1, wherein the rheology auxiliary agent is one or more of acrylic acid esters, polysiloxanes, fluorocarbons and polyether organic solvents.
7. The curable polyphenylene ether-containing composition according to claim 1, wherein the solvent is one or more of benzene, toluene, xylene, chloroform, 1, 2-dichloroethane, trichloroethane, trichloroethylene, carbon tetrachloride, chlorobenzene, dichlorobenzene, and butanone.
8. Use of a curable polyphenylene ether-containing composition according to any one of claims 1 to 7, characterized in that: transferring the composition to a dipping tank; then the substrate is completely immersed in a gum dipping tank, and the gum solution enters the substrate to finish the gum dipping process under the action of a gum dipping roller in the gum dipping tank; then extruding the impregnated matrix by a squeeze roller to ensure that the impregnation amount of the matrix is 40-70%, and baking for 1-5 minutes at the temperature of 100-180 ℃ to obtain a prepreg;
the matrix is organic fiber fabric, organic fiber non-woven fabric, electronic grade glass fiber fabric or electronic grade glass fiber non-woven fabric.
9. The use according to claim 8, wherein a plurality of prepregs are laminated together, and then copper foil is covered on one side or both sides of the laminated cured sheets, and then the copper-clad plate with single-sided copper or double-sided copper is formed by pressing with a hot press;
The copper foil is an electrolytic copper foil or a rolled copper foil, and the surface roughness of the copper foil is less than 5 microns.
10. The use according to claim 9, wherein the glass transition temperature of the copper-clad plate is 195-215 ℃, the 1% thermal weight loss temperature Td is 370-380 ℃, and the Z-axis thermal expansion coefficient Z-CTE is 29-35 ppm/°c; the dielectric constant is 3.5-3.8 under the frequency of 10GHz, and the dielectric loss is 0.00319-0.00370; the ASTM-D5470 standard test heat conductivity is 0.7-1.0W/m.K, and the UL94 method test flame retardant rating is V0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111037930.0A CN113773632B (en) | 2021-09-06 | 2021-09-06 | Composition containing curable polyphenyl ether resin and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111037930.0A CN113773632B (en) | 2021-09-06 | 2021-09-06 | Composition containing curable polyphenyl ether resin and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113773632A CN113773632A (en) | 2021-12-10 |
| CN113773632B true CN113773632B (en) | 2023-11-14 |
Family
ID=78841213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111037930.0A Active CN113773632B (en) | 2021-09-06 | 2021-09-06 | Composition containing curable polyphenyl ether resin and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113773632B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980288B (en) * | 2021-12-23 | 2022-05-13 | 山东海科创新研究院有限公司 | Purification process and purification system for polymer |
| CN114989592A (en) * | 2022-05-25 | 2022-09-02 | 上海科特新材料股份有限公司 | Cross-linked polyphenyl ether high-frequency copper clad plate material and preparation method thereof |
| TWI828197B (en) * | 2022-06-16 | 2024-01-01 | 南亞塑膠工業股份有限公司 | Rubber resin material and metal substrate using the same |
| CN117447696A (en) * | 2023-10-25 | 2024-01-26 | 东莞联茂电子科技有限公司 | Curable polyphenylene ether resin, resin composition and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000133648A (en) * | 1998-10-23 | 2000-05-12 | Sumitomo Chem Co Ltd | Coating liquid for insulating film formation |
| CN102807658A (en) * | 2012-08-09 | 2012-12-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite |
| CN104263306A (en) * | 2014-09-26 | 2015-01-07 | 四川东材科技集团股份有限公司 | Preparation method of polyphenyl ether adhesive and copper-clad plate thereof |
| CN104744687A (en) * | 2015-04-16 | 2015-07-01 | 腾辉电子（苏州）有限公司 | Preparation method of low-molecular-weight polyphenyl ether |
| KR20190004131A (en) * | 2017-07-03 | 2019-01-11 | 국도화학 주식회사 | Multifunctional radical curable poly phenylene ether resin and preparation method of the same |
| CN110002963A (en) * | 2019-03-11 | 2019-07-12 | 陕西硕博电子材料有限公司 | A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide |
| CN111592750A (en) * | 2019-02-20 | 2020-08-28 | 元鸿应用材料股份有限公司 | Resin, copper foil substrate made of the same, and printed wiring board |
| CN111909371A (en) * | 2020-07-22 | 2020-11-10 | 广东省石油与精细化工研究院 | Tetrallyl polyphenylene oxide and preparation method thereof |
| CN113337098A (en) * | 2021-06-28 | 2021-09-03 | 广东生益科技股份有限公司 | Thermosetting resin composition and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928446B (en) * | 2015-12-30 | 2019-08-13 | 台光电子材料(昆山)有限公司 | Modify polyphenylene oxide resin, preparation method and resin combination |
-
2021
- 2021-09-06 CN CN202111037930.0A patent/CN113773632B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000133648A (en) * | 1998-10-23 | 2000-05-12 | Sumitomo Chem Co Ltd | Coating liquid for insulating film formation |
| CN102807658A (en) * | 2012-08-09 | 2012-12-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite |
| CN104263306A (en) * | 2014-09-26 | 2015-01-07 | 四川东材科技集团股份有限公司 | Preparation method of polyphenyl ether adhesive and copper-clad plate thereof |
| CN104744687A (en) * | 2015-04-16 | 2015-07-01 | 腾辉电子（苏州）有限公司 | Preparation method of low-molecular-weight polyphenyl ether |
| KR20190004131A (en) * | 2017-07-03 | 2019-01-11 | 국도화학 주식회사 | Multifunctional radical curable poly phenylene ether resin and preparation method of the same |
| CN111592750A (en) * | 2019-02-20 | 2020-08-28 | 元鸿应用材料股份有限公司 | Resin, copper foil substrate made of the same, and printed wiring board |
| CN110002963A (en) * | 2019-03-11 | 2019-07-12 | 陕西硕博电子材料有限公司 | A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide |
| CN111909371A (en) * | 2020-07-22 | 2020-11-10 | 广东省石油与精细化工研究院 | Tetrallyl polyphenylene oxide and preparation method thereof |
| CN113337098A (en) * | 2021-06-28 | 2021-09-03 | 广东生益科技股份有限公司 | Thermosetting resin composition and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Yijian Wu,等.Synthesis and Characterization of α,ω-bis(2,6-dimethylphenol)-poly(2,6-dimethyl-1,4-phenylene oxide) Oligomers in Water and the End-Group Modification.《Ind. Eng. Chem. Res.》.2013,第52卷(第49期),第17351-17359页. * |
| 热固改性聚苯醚高频复合介质材料研究;胡婉霞;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第8期);第14页第2段、第19页第2.2.1节、第69页第5.1节 * |
| 王佳丽, 等.α,ω-双(2,6-二甲基羟苯基)聚苯醚树脂.《热固性树脂》.2005,(第4期),第32-35页. * |
| 聚苯醚基覆铜板热性能和介电性能研究;朱新军, 等;《广东化工》;第49卷(第20期);第47-49页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113773632A (en) | 2021-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113773632B (en) | Composition containing curable polyphenyl ether resin and application thereof | |
| KR101716990B1 (en) | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite | |
| JP5181221B2 (en) | Low thermal expansion low dielectric loss prepreg and its application | |
| ES2655275T3 (en) | Composite material and high frequency circuit substrate manufactured with the composite material and its manufacturing method | |
| CN111959063A (en) | Low-dielectric halogen-free flame-retardant copper-clad plate and manufacturing method thereof | |
| CN107227015B (en) | Low dielectric material | |
| JP2008303382A (en) | Poly/(phenylene ether) resin composition, prepreg, and laminated sheet | |
| CN110655775B (en) | Resin composition, and prepreg, laminated board and printed wiring board provided with same | |
| EP2291061A2 (en) | Composite material, high frequency circuit substrate made therefrom and making method thereof | |
| CN113698592B (en) | Curable polyphenyl ether resin and preparation method thereof | |
| US11377551B2 (en) | Thermosetting resin composition, prepreg made therefrom, laminate clad with metal foil, and high-frequency circuit board | |
| EP3660026A1 (en) | Thermosetting resin composition, prepreg made therefrom, laminate clad with metal foil, and high-frequency circuit board | |
| TW201428055A (en) | Dielectric material with low dielectric loss | |
| CN114634713B (en) | Resin composition, prepreg and metal-clad laminate | |
| EP3733399B1 (en) | Block copolymer composition, prepregs, and laminates made therefrom | |
| US20230045848A1 (en) | Thermosetting resin composition and prepreg, laminate and printed circuit board using same | |
| CN114106267B (en) | Thermosetting resin composition containing styrene compound and preparation method and application thereof | |
| KR100867661B1 (en) | Thermally Curable Resin Composition Having Low Dielectric Constant and Low Dielectric Loss in High Frequency Range | |
| CN116285378A (en) | Resin composition, adhesive sheet containing same, and metal foil-clad laminate | |
| JP6219112B2 (en) | PPE-containing resin composition | |
| TWI618097B (en) | Low dielectric material | |
| KR102600976B1 (en) | Phosphorous compound | |
| JP2866661B2 (en) | Thermosetting resin composition, prepreg and laminate using the same | |
| CN113214461B (en) | Active ester resin and resin composition thereof | |
| CN110643131B (en) | Resin composition, and prepreg, laminated board and printed wiring board provided with same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |